Nitrogen containing hydrofluoroethers and methods of using same

ABSTRACT

A hydrofluoroether compound is represented by the following general formula (1): wherein n is 1-2.

FIELD

The present disclosure relates to nitrogen containing hydrofluoroethersand methods of making and using the same.

BACKGROUND

Various hydrofluoroether compounds are described in, for example, U.S.Published Application 2007/0051916, U.S. Published Application2007/0054186, and in Jean'ne M. Shreeve, et. al., Z. Anorg. Allg. Chem.,621 (1995) 1865-1874.

SUMMARY

In some embodiments, a hydrofluoroether compound is provided. Thehydrofluoroether compound is represented by the following generalformula (1):

wherein n is 1-2, and each occurrence of Rf₁ and Rf₂ is:

-   -   (i) independently a linear or branched perfluoroalkyl group        having 1-8 carbon and optionally comprises one or more catenated        heteroatoms; or    -   (ii) bonded together to form a ring structure having 4-8 carbon        atoms and optionally comprises one or more catenated        heteroatoms; and

Rfh is, when n=1, a substituted or unsubstituted, monovalent,hydrocarbon group having 1-12 carbon atoms optionally comprising one ormore catenary heteroatoms and, when n=2, a substituted or unsubstituted,divalent, hydrocarbon group having 1-12 carbon atoms optionallycomprising one or more catenary heteroatoms.

In some embodiments, a working fluid is provided. The working fluidincludes the above-described hydrofluoroether compound. Thehydrofluoroether compound is present in the working fluid at an amountof at least 50% by weight based on the total weight of the workingfluid.

In some embodiments, an apparatus for heat transfer is provided. Theapparatus includes a device, and a mechanism for transferring heat to orfrom the device. The mechanism further includes a heat transfer fluidthat includes the above-described hydrofluoroether compound.

In some embodiments, a method of transferring heat is provided. Themethod includes providing a device and transferring heat to or from thedevice using a heat transfer fluid that includes the above-describedhydrofluoroether compound.

The above summary of the present disclosure is not intended to describeeach embodiment of the present disclosure. The details of one or moreembodiments of the disclosure are also set forth in the descriptionbelow. Other features, objects, and advantages of the disclosure will beapparent from the description and from the claims.

DETAILED DESCRIPTION

In view of an increasing demand for environmentally friendly and loxtoxicity chemical compounds, it is recognized that there exists anongoing need for new working fluids exhibiting further reductions inenvironmental impact and toxicity, and which can meet the performancerequirements (e.g., nonflammability, solvency, and operating temperaturerange) of a variety of different applications (e.g., heat transfer,solvent cleaning, deposition coating solvents, and electrolyte solventsand additives), and be manufactured cost-effectively.

As used herein, “catenated heteroatom” means an atom other than carbon(for example, oxygen, nitrogen, or sulfur) that is bonded to at leasttwo carbon atoms in a carbon chain (linear or branched or within a ring)so as to form a carbon-heteroatom-carbon linkage.

As used herein, “fluoro-” (for example, in reference to a group ormoiety, such as in the case of “fluoroalkylene” or “fluoroalkyl” or“fluorocarbon”) or “fluorinated” means only partially fluorinated suchthat there is at least one carbon-bonded hydrogen atom.

As used herein, “perfluoro-” (for example, in reference to a group ormoiety, such as in the case of “perfluoroalkylene” or “perfluoroalkyl”or “perfluorocarbon”) or “perfluorinated” means completely fluorinatedsuch that, except as may be otherwise indicated, there are nocarbon-bonded hydrogen atoms replaceable with fluorine.

As used herein, “substituted” (in reference to a group or moiety) meansthat at least one carbon-bonded hydrogen atom is replaced with a halogenatom. Halogen atoms may include F, Cl, Br, and I.

As used herein, a “segregated hydrofluoroether” means a hydrofluoroetherwhose segments (such as alkyl or alkylene segments) linked via an etheroxygen are either perfluorinated or not fluorinated, and thus are notpartially fluorinated.

As used herein, a “non-segregated hydrofluoroether” means ahydrofluoroether having one or both of the segments (such as alkyl oralkylene segments) linked via an ether oxygen that is partiallyfluorinated.

As used herein, the singular forms “a”, “an”, and “the” include pluralreferents unless the content clearly dictates otherwise. As used in thisspecification and the appended embodiments, the term “or” is generallyemployed in its sense including “and/or” unless the content clearlydictates otherwise.

As used herein, the recitation of numerical ranges by endpoints includesall numbers subsumed within that range (e.g. 1 to 5 includes 1, 1.5, 2,2.75, 3, 3.8, 4, and 5).

Unless otherwise indicated, all numbers expressing quantities oringredients, measurement of properties and so forth used in thespecification and embodiments are to be understood as being modified inall instances by the term “about.” Accordingly, unless indicated to thecontrary, the numerical parameters set forth in the foregoingspecification and attached listing of embodiments can vary dependingupon the desired properties sought to be obtained by those skilled inthe art utilizing the teachings of the present disclosure. At the veryleast, and not as an attempt to limit the application of the doctrine ofequivalents to the scope of the claimed embodiments, each numericalparameter should at least be construed in light of the number ofreported significant digits and by applying ordinary roundingtechniques.

In some embodiments, the present disclosure is directed tohydrofluoroether compounds represented by the following general formula(1):

In some embodiments, n is 1-2. As can be understood with reference togeneral formula (1), when n=1, the hydrofluoroether compounds may berepresented by the following general formula (1A), and when n=2, thehydrofluoroether compounds may be represented by the following generalformula (1B):

In some embodiments, each occurrence of Rf₁ and Rf₂ may be (i)independently a linear or branched perfluoralkyl group having 1-8, 1-6,or 1-4 carbon atoms and optionally comprise one or more catenatedheteroatoms; or (ii) bonded together to form a ring structure having 4-8or 4-6 carbon atoms and optionally comprise one or more catenatedheteroatoms. In some embodiments, the catenated heteroatoms of the ringstructure are selected from oxygen and nitrogen.

In some embodiments, when n=1, Rfh may be a monovalent, hydrocarbongroup of 1-12, 1-6, or 1-3 carbon atoms that may be substituted orunsubstituted, saturated or unsaturated, linear or branched, cyclic oracyclic, and may optionally contain one or more catenanted heteroatoms.

In some embodiments, when n=2, Rfh may be a divalent, hydrocarbon groupof 1-12, 2-6, or 2-4 carbon atoms that may be substituted orunsubstituted, saturated or unsaturated, linear or branched, cyclic oracyclic, and may optionally contain one or more catenanted heteroatoms.

In various embodiments, the hydrogen atoms in Rfh can be partiallysubstituted with halogen atoms. The halogen atoms may include F, Cl, Br,and I. The catenated heteroatoms may include but are not limited to N,O, and S. In some embodiments, the halogen content in the compounds ofgeneral formula (1) may be sufficient to make the hydrofluoroethernon-flammable according to ASTM D-3278-96 e-1 test method (“Flash Pointof Liquids by Small Scale Closed Cup Apparatus”).

In some embodiments, when n=1, examples of suitable Rfh groups include—CH₃, —C₂H₅, —C₃H₇, —CH₂CH═CH₂, —CH₂C≡CH, —CH₂CH₂OCH₃, —CH₂CF₃,—CH₂C₂F₅, —CH(CF₃)₂, —CH₂C₃F₇, —CH₂CF₂CFHCF₃, —CH(CH₃)CF₂CFHCF₃,—CH₂(CF₂CF₂)_(a)H (where a=1-3), and —CH₂CH₂(CF₂)_(b)F (where b=1-8).

In some embodiments, when n=2, examples of suitable Rfh groups include—CH₂CF₂CF₂CH₂—, —CH₂CH₂CH₂CH₂—, —CH₂CH═CHCH₂—, and —CH₂CH₂OCH₂CH₂—.

In some embodiments, the hydrofluoroethers of the present disclosure mayhave a degree of fluorination that is at least 40%, 50%, 60%, or 70%. Inother words at least 40%, 50%, 60%, or 70% of the hydrogen atoms in thehydrocarbon chain(s) are replaced by fluorine atoms.

In some embodiments, any of the above discussed catentated heteroatomsmay be secondary O heteroatoms wherein the O is bonded to two carbonatoms. In some embodiments, any of the above discussed catenatedheteroatoms may be tertiary N heteroatoms wherein the N is bonded tothree perfluorinated carbon atoms. In some embodiments, any of the abovediscussed catenated heteroatoms may be secondary S heteroatoms whereinthe S is bonded to two perfluorinated carbon atoms, and the remainingvalences on S, if present, are occupied by F.

In various embodiments, representative examples of the compounds ofgeneral formula (1) include the following:

In some embodiments, the hydrofluoroether compounds of the presentdisclosure may be hydrophobic, relatively chemically unreactive, andthermally stable. The hydrofluoroether compounds may have a lowenvironmental impact. In this regard, the hydrofluoroether compounds ofthe present disclosure may have a global warming potential (GWP) of lessthan 500, 300, 200, 100 or even less than 10. As used herein, GWP is arelative measure of the warming potential of a compound based on thestructure of the compound. The GWP of a compound, as defined by theIntergovernmental Panel on Climate Change (IPCC) in 1990 and updated in2007, is calculated as the warming due to the release of 1 kilogram of acompound relative to the warming due to the release of 1 kilogram of CO₂over a specified integration time horizon (ITH).

${{GWP}_{i}( t^{\prime} )} = {\frac{\int_{0}^{ITH}{{a_{i}\lbrack {C(t)} \rbrack}\ {dt}}}{\int_{0}^{ITH}{{a_{{CO}_{2}}\lbrack {C_{{CO}_{2}}(t)} \rbrack}\ {dt}}} = \frac{\int_{0}^{ITH}{a_{i}C_{oi}e^{{- t}/\tau_{i}}{dt}}}{\int_{0}^{ITH}{{a_{{CO}_{2}}\lbrack {C_{{CO}_{2}}(t)} \rbrack}\ {dt}}}}$

In this equation a, is the radiative forcing per unit mass increase of acompound in the atmosphere (the change in the flux of radiation throughthe atmosphere due to the IR absorbance of that compound), C is theatmospheric concentration of a compound, τ is the atmospheric lifetimeof a compound, t is time, and i is the compound of interest. Thecommonly accepted ITH is 100 years representing a compromise betweenshort-term effects (20 years) and longer-term effects (500 years orlonger). The concentration of an organic compound, i, in the atmosphereis assumed to follow pseudo first order kinetics (i.e., exponentialdecay). The concentration of CO₂ over that same time intervalincorporates a more complex model for the exchange and removal of CO₂from the atmosphere (the Bern carbon cycle model).

In some embodiments, the hydrofluoroethers of the present disclosure maybe characterized as a new class of hydrofluoroethers, which have similarphysical properties to that of known hydrofluoroethers (e.g., knownsegregated hydrofluoroethers), but which exhibit improved solvency forparticular solutes (e.g., polar and nonpolar solutes) and improvedmiscibility with polar organic solvents and organic electrolyteformulations. Moreover, surprisingly, in accordance with someembodiments, the hydrofluoroethers of the present disclosure, which maybe non-segregated hydrofluoroethers, provide low acute toxicity based on4 hour acute inhalation or oral toxicity studies in rats (conventionalwisdom has suggested that non-segregated hydrofluoroethers do notprovide low toxicity). Still further, as will be discussed in furtherdetail below, in some embodiments, the hydrofluoroethers of the presentdisclosure can be produced using perfluorinated vinyl amines, arelatively low cost intermediate available from the correspondingperfluorinated acid fluoride precursors.

In some embodiments, the hydrofluoroether compounds of the presentdisclosure can be prepared by the addition of an alcohol to aperfluorinated vinyl amine as illustrated in Scheme 1.

Generally, this reaction may produce the desired hydrofluoroether (orHFE-Hydride) compounds of the present disclosure as the major product,although relatively small amounts of the correspondinghydrofluoroether-olefin (or HFE-Olefin) byproduct may be produced aswell. The hydrofluoroether-olefin byproduct can be readily convertedback to the desired hydrofluoroether by treatment with ahydrofluorinating agent, such as anhydrous hydrogen fluoride (AHF),ultimately producing high yields of the desired hydrofluoroethercompounds.

In some embodiments, the alcohol addition reaction shown in Scheme 1 canbe effected by combining the perfluorinated vinyl amine startingcompound and the starting alcohol in the presence of at least one basiccatalyst (for example, a Lewis base). Useful catalysts include potassiumcarbonate, cesium carbonate, potassium fluoride, potassium hydroxide,potassium methoxide, triethylamine, trimethylamine, potassium cyanate,potassium bicarbonate, sodium carbonate, sodium bicarbonate, sodiummethoxide, cesium fluoride, potassium bifluoride, potassium acetate, andthe like, and mixtures thereof; with potassium carbonate, potassiumbicarbonate, and mixtures thereof being preferred. A small amount of analkali metal salt of the starting alcohol can also be used as acatalyst.

In some embodiments, the reactants and catalyst can be combined in areactor (for example, a glass reactor or a metal pressure reactor) inany order, and the reaction can be run at a desired temperature (forexample, from about −20° C. to about 75° C.) under the above describedconditions with agitation. Generally, however, use of a non-reactive,polar solvent (for example, acetonitrile, acetone, 2-butanone (MEK),tetrahydrofuran, glyme, or a mixture of two or more thereof) canfacilitate the reaction. The resulting product can be purified by, forexample, distillation. Olefinic reaction by-products (like HFE-Olefins)can be removed (or converted to desired product) by reaction with areagent that will preferentially react with the olefinic double bond.Such reagents include, for example, anhydrous hydrogen fluoride;potassium bifluoride in a polar, aprotic solvent (with or without aphase transfer catalyst); potassium permanganate in acetone; andelemental bromine with or without irradiation.

In some embodiments, the perfluorinated vinyl amine starting compoundscan be prepared by any of a variety of standard synthetic proceduresthat are well known in the art such as those described in T. Abe, E.Hayashi, H. Baba, H. Fukaya, J. Fluorine Chem. 48 (1990) 257; T. Abe, E.Hayashi, H. Fukaya, H. Baba, J. Fluorine Chem. 50 (1990) 173; T. Abe, E.Hayashi, T. Shimizu, Chem. Lett. 1989, 905; T. Abe, U.S. Pat. No.4,782,148; and T. Abe, E. Hayashi, Chem. Lett. 1988, 1887.

In some embodiments, representative examples of perfluorinated vinylamines useful as starting compounds for preparing thenitrogen-containing hydrofluoroether compounds of the present disclosureinclude:

In some embodiments, alcohols that are useful as starting compounds forpreparing the nitrogen-containing hydrofluoroether compounds of thepresent disclosure can be monofunctional or polyfunctional alcohols. Incertain embodiments, the alcohols are monofunctional or difunctional.Representative examples of suitable alcohols include methanol, ethanol,isopropanol, 1-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol,2-methoxyethanol, allyl alcohol, propargyl alcohol, tetrahydrofurfurylalcohol, ethylene glycol, 1,4-butanediol, 2-butene-1,4-diol,diethyleneglycol, (CH₃)₂NC₂H₄OH, CF₃CH₂OH, C₂F₅CH₂OH, C₃F₇CH₂OH,(CF₃)₂CHOH, HCF₂CF₂CH₂OH, H(CF₂CF₂)₂CH₂OH, H(CF₂CF₂)₃CH₂OH,CF₃CFHCF₂CH₂OH, CF₃CFHCF₂CH(CH₃)OH, C₄F₉CH₂CH₂OH, C₆F₁₃CH₂CH₂OH,C₈F₁₇CH₂CH₂OH, C₄F₉OCH₂CH₂OH, HOCH₂CF₂CF₂CH₂OH, and the like.

In some embodiments, the alcohols include methanol, ethanol, 1-propanol,1-butanol, 2-methoxyethanol, allyl alcohol, (CH₃)₂NC₂H₄OH, ethyleneglycol, 1,4-butanediol, 2-butene-1,4-diol, diethylene glycol, CF₃CH₂OH,HCF₂CF₂CH₂OH, H(CF₂CF₂)₂CH₂OH, CF₃CFHCF₂CH₂OH, CF₃CFHCF₂CH(CH₃)OH,C₄F₉CH₂CH₂OH and HOCH₂CF₂CF₂CH₂OH.

In some embodiments, the present disclosure is further directed toworking fluids that include the above-described hydrofluoroethercompounds as a major component. For example, the working fluids mayinclude at least 25%, at least 50%, at least 70%, at least 80%, at least90%, at least 95%, or at least 99% by weight of the above-describedhydrofluoroether compounds based on the total weight of the workingfluid. In addition to the hydrofluoroether compounds, the working fluidsmay include a total of up to 75%, up to 50%, up to 30%, up to 20%, up to10%, or up to 5% by weight of one or more of the following components:alcohols, ethers, alkanes, alkenes, perfluorocarbons, perfluorinatedtertiary amines, perfluoroethers, cycloalkanes, esters, ketones,oxiranes, aromatics, siloxanes, hydrochlorocarbons,hydrochlorofluorocarbons, hydrofluorocarbons, hydrofluoroolefins,hydrochlorofluoroolefins, hydrofluoroethers, or mixtures thereof, basedon the total weight of the working fluid. Such additional components canbe chosen to modify or enhance the properties of a composition for aparticular use.

In some embodiments, the present disclosure is further directed to anapparatus for heat transfer that includes a device and a mechanism fortransferring heat to or from the device. The mechanism for transferringheat may include a heat transfer working fluid that includes ahydrofluoroether compound of the present disclosure.

The provided apparatus for heat transfer may include a device. Thedevice may be a component, work-piece, assembly, etc. to be cooled,heated or maintained at a predetermined temperature or temperaturerange. Such devices include electrical components, mechanical componentsand optical components. Examples of devices of the present disclosureinclude, but are not limited to microprocessors, wafers used tomanufacture semiconductor devices, power control semiconductors,electrical distribution switch gear, power transformers, circuit boards,multi-chip modules, packaged and unpackaged semiconductor devices,lasers, chemical reactors, fuel cells, and electrochemical cells. Insome embodiments, the device can include a chiller, a heater, or acombination thereof.

In yet other embodiments, the devices can include electronic devices,such as processors, including microprocessors. As these electronicdevices become more powerful, the amount of heat generated per unit timeincreases. Therefore, the mechanism of heat transfer plays an importantrole in processor performance. The heat-transfer fluid typically hasgood heat transfer performance, good electrical compatibility (even ifused in “indirect contact” applications such as those employing coldplates), as well as low toxicity, low (or non-) flammability and lowenvironmental impact. Good electrical compatibility suggests that theheat-transfer fluid candidate exhibit high dielectric strength, highvolume resistivity, and poor solvency for polar materials. Additionally,the heat-transfer fluid should exhibit good mechanical compatibility,that is, it should not affect typical materials of construction in anadverse manner.

The provided apparatus may include a mechanism for transferring heat.The mechanism may include a heat transfer fluid. The heat transfer fluidmay include one or more hydrofluoroether compounds of the presentdisclosure. Heat may be transferred by placing the heat transfermechanism in thermal contact with the device. The heat transfermechanism, when placed in thermal contact with the device, removes heatfrom the device or provides heat to the device, or maintains the deviceat a selected temperature or temperature range. The direction of heatflow (from device or to device) is determined by the relativetemperature difference between the device and the heat transfermechanism.

The heat transfer mechanism may include facilities for managing theheat-transfer fluid, including, but not limited to pumps, valves, fluidcontainment systems, pressure control systems, condensers, heatexchangers, heat sources, heat sinks, refrigeration systems, activetemperature control systems, and passive temperature control systems.Examples of suitable heat transfer mechanisms include, but are notlimited to, temperature controlled wafer chucks in plasma enhancedchemical vapor deposition (PECVD) tools, temperature-controlled testheads for die performance testing, temperature-controlled work zoneswithin semiconductor process equipment, thermal shock test bath liquidreservoirs, and constant temperature baths. In some systems, such asetchers, ashers, PECVD chambers, vapor phase soldering devices, andthermal shock testers, the upper desired operating temperature may be ashigh as 170° C., as high as 200° C., or even as high as 230° C.

Heat can be transferred by placing the heat transfer mechanism inthermal contact with the device. The heat transfer mechanism, whenplaced in thermal contact with the device, removes heat from the deviceor provides heat to the device, or maintains the device at a selectedtemperature or temperature range. The direction of heat flow (fromdevice or to device) is determined by the relative temperaturedifference between the device and the heat transfer mechanism. Theprovided apparatus can also include refrigeration systems, coolingsystems, testing equipment and machining equipment. In some embodiments,the provided apparatus can be a constant temperature bath or a thermalshock test bath.

In some embodiments, the present disclosure is directed to a fireextinguishing composition. The composition may include one or morehydrofluoroether compound of the present disclosure and one or moreco-extinguishing agents.

In illustrative embodiments, the co-extinguishing agent may includehydrofluorocarbons, hydrochlorofluorocarbons, perfluorocarbons,perfluoropolyethers, hydrofluoroethers, hydrofluoropolyethers,chlorofluorocarbons, bromofluorocarbons, bromochlorofluorocarbons,hydrobromocarbons, iodofluorocarbons, fluorinated ketones,hydrofluorocarbons, hydrochlorofluorocarbons, perfluorocarbons,perfluoropolyethers, hydrofluoroethers, hydrofluoropolyethers,chlorofluorocarbons, bromofluorocarbons, bromochlorofluorocarbons,iodofluorocarbons, hydrobromofluorocarbons, fluorinated ketones,hydrobromocarbons, fluorinated olefins, hydrofluoroolefins, fluorinatedsulfones, fluorinated vinylethers, unsaturated fluoro-ethers,bromofluoroolefins, chlorofluorolefins, iodofluoroolefins, fluorinatedvinyl amines, fluorinated aminopropenes and mixtures thereof.

Such co-extinguishing agents can be chosen to enhance the extinguishingcapabilities or modify the physical properties (e.g., modify the rate ofintroduction by serving as a propellant) of an extinguishing compositionfor a particular type (or size or location) of fire and can preferablybe utilized in ratios (of co-extinguishing agent to hydrofluoroethercompound) such that the resulting composition does not form flammablemixtures in air.

In some embodiments, the hydrofluoroether compounds and theco-extinguishing agent may be present in the fire extinguishingcomposition in amounts sufficient to suppress or extinguish a fire. Thehydrofluoroether compounds and the co-extinguishing agent can be in aweight ratio of from about 9:1 to about 1:9.

In some embodiments, the present disclosure is directed to an apparatusfor converting thermal energy into mechanical energy in a Rankine cycle.The apparatus may include a working fluid that includes one or morehydrofluoroether compounds of the present disclosure. The apparatus mayfurther include a heat source to vaporize the working fluid and form avaporized working fluid, a turbine through which the vaporized workingfluid is passed thereby converting thermal energy into mechanicalenergy, a condenser to cool the vaporized working fluid after it ispassed through the turbine, and a pump to recirculate the working fluid.

In some embodiments, the present disclosure relates to a process forconverting thermal energy into mechanical energy in a Rankine cycle. Theprocess may include using a heat source to vaporize a working fluid thatincludes one or more hydrofluoroether compounds of the presentdisclosure to form a vaporized working fluid. In some embodiments, theheat is transferred from the heat source to the working fluid in anevaporator or boiler. The vaporized working fluid may pressurized andcan be used to do work by expansion. The heat source can be of any formsuch as from fossil fuels, e.g., oil, coal, or natural gas.Additionally, in some embodiments, the heat source can come from nuclearpower, solar power, or fuel cells. In other embodiments, the heat can be“waste heat” from other heat transfer systems that would otherwise belost to the atmosphere. The “waste heat,” in some embodiments, can beheat that is recovered from a second Rankine cycle system from thecondenser or other cooling device in the second Rankine cycle.

An additional source of “waste heat” can be found at landfills wheremethane gas is flared off. In order to prevent methane gas from enteringthe environment and thus contributing to global warming, the methane gasgenerated by the landfills can be burned by way of “flares” producingcarbon dioxide and water which are both less harmful to the environmentin terms of global warming potential than methane. Other sources of“waste heat” that can be useful in the provided processes are geothermalsources and heat from other types of engines such as gas turbine enginesthat give off significant heat in their exhaust gases and to coolingliquids such as water and lubricants.

In the provided process, the vaporized working fluid may expanded thougha device that can convert the pressurized working fluid into mechanicalenergy. In some embodiments, the vaporized working fluid is expandedthrough a turbine which can cause a shaft to rotate from the pressure ofthe vaporized working fluid expanding. The turbine can then be used todo mechanical work such as, in some embodiments, operate a generator,thus generating electricity. In other embodiments, the turbine can beused to drive belts, wheels, gears, or other devices that can transfermechanical work or energy for use in attached or linked devices.

After the vaporized working fluid has been converted to mechanicalenergy the vaporized (and now expanded) working fluid can be condensedusing a cooling source to liquefy for reuse. The heat released by thecondenser can be used for other purposes including being recycled intothe same or another Rankine cycle system, thus saving energy. Finally,the condensed working fluid can be pumped by way of a pump back into theboiler or evaporator for reuse in a closed system.

The desired thermodynamic characteristics of organic Rankine cycleworking fluids are well known to those of ordinary skill and arediscussed, for example, in U.S. Pat. Appl. Publ. No. 2010/0139274(Zyhowski et al.). The greater the difference between the temperature ofthe heat source and the temperature of the condensed liquid or aprovided heat sink after condensation, the higher the Rankine cyclethermodynamic efficiency. The thermodynamic efficiency is influenced bymatching the working fluid to the heat source temperature. The closerthe evaporating temperature of the working fluid to the sourcetemperature, the higher the efficiency of the system. Toluene can beused, for example, in the temperature range of 79° C. to about 260° C.,however toluene has toxicological and flammability concerns. Fluids suchas 1,1-dichloro-2,2,2-trifluoroethane and 1,1,1,3,3-pentafluoropropanecan be used in this temperature range as an alternative. But1,1-dichloro-2,2,2-trifluoroethane can form toxic compounds below 300°C. and need to be limited to an evaporating temperature of about 93° C.to about 121° C. Thus, there is a desire for otherenvironmentally-friendly Rankine cycle working fluids with highercritical temperatures so that source temperatures such as gas turbineand internal combustion engine exhaust can be better matched to theworking fluid.

The present disclosure relates to the use of the hydrofluoroethercompounds of the present disclosure as nucleating agents in theproduction of polymeric foams and in particular in the production ofpolyurethane foams and phenolic foams. In this regard, in someembodiments, the present disclosure is directed to a foamablecomposition that includes one or more blowing agents, one or morefoamable polymers or precursor compositions thereof, and one or morenucleating agents that include a hydrofluoroether compound of thepresent disclosure.

In some embodiments, a variety of blowing agents may be used in theprovided foamable compositions including liquid or gaseous blowingagents that are vaporized in order to foam the polymer or gaseousblowing agents that are generated in situ in order to foam the polymer.Illustrative examples of blowing agents include hydrochlorofluorocarbons(HCFCs), hydrofluorocarbons (HFCs), hydrochlorocarbons (HCCs),iodofluorocarbons (IFCs), hydrocarbons, hydrofluoroolefins (HFOs) andhydrofluoroethers (HFEs). The blowing agent for use in the providedfoamable compositions can have a boiling point of from about −45° C. toabout 100° C. at atmospheric pressure. Typically, at atmosphericpressure the blowing agent has a boiling point of at least about 15° C.,more typically between about 20° C. and about 80° C. The blowing agentcan have a boiling point of between about 30° C. and about 65° C.Further illustrative examples of blowing agents that can be used in theinvention include aliphatic and cycloaliphatic hydrocarbons having about5 to about 7 carbon atoms, such as n-pentane and cyclopentane, esterssuch as methyl formate, HFCs such as CF₃CF₂CHFCHFCF₃, CF₃CH₂CF₂H,CF₃CH₂CF₂CH₃, CF₃CF₂H, CH₃CF₂H (HFC-152a), CF₃CH₂CH₂CF₃ and CHF₂CF₂CH₂F,HCFCs such as CH₃CCl₂F, CF₃CHCl₂, and CF₂HCl, HCCs such as2-chloropropane, and IFCs such as CF₃I, and HFEs such as C₄F₉OCH₃ andHFOs such as CF₃CF═CH₂, CF₃CH═CHF, CF₃CH═CHCl and CF₃CH═CHCF₃ In certainformulations CO₂ generated from the reaction of water with foamprecursor such as an isocyanate can be used as a blowing agent.

In various embodiments, the provided foamable composition may alsoinclude one or more foamable polymers or a precursor compositionthereof. Foamable polymers suitable for use in the provided foamablecompositions include, for example, polyolefins, e.g., polystyrene,poly(vinyl chloride), and polyethylene. Foams can be prepared fromstyrene polymers using conventional extrusion methods. The blowing agentcomposition can be injected into a heat-plastified styrene polymerstream within an extruder and admixed therewith prior to extrusion toform foam. Representative examples of suitable styrene polymers include,for example, the solid homopolymers of styrene, α-methylstyrene,ring-alkylated styrenes, and ring-halogenated styrenes, as well ascopolymers of these monomers with minor amounts of other readilycopolymerizable olefinic monomers, e.g., methyl methacrylate,acrylonitrile, maleic anhydride, citraconic anhydride, itaconicanhydride, acrylic acid, N-vinylcarbazole, butadiene, anddivinylbenzene. Suitable vinyl chloride polymers include, for example,vinyl chloride homopolymer and copolymers of vinyl chloride with othervinyl monomers. Ethylene homopolymers and copolymers of ethylene with,e.g., 2-butene, acrylic acid, propylene, or butadiene may also beuseful. Mixtures of different types of polymers can be employed.

In various embodiments, the foamable compositions of the presentdisclosure may have a molar ratio of nucleating agent to blowing agentof no more than 1:50, 1:25, 1:9, or 1:7, 1:3, or 1:2.

Other conventional components of foam formulations can, optionally, bepresent in the foamable compositions of the present disclosure. Forexample, cross-linking or chain-extending agents, foam-stabilizingagents or surfactants, catalysts and fire-retardants can be utilized.Other possible components include fillers (e.g., carbon black),colorants, fungicides, bactericides, antioxidants, reinforcing agents,antistatic agents, and other additives or processing aids.

In some embodiments, polymeric foams can be prepared by vaporizing atleast one liquid or gaseous blowing agent or generating at least onegaseous blowing agent in the presence of at least one foamable polymeror a precursor composition thereof and a nucleating agent as describedabove. In further embodiments, polymeric foams can be prepared using theprovided foamable compositions by vaporizing (e.g., by utilizing theheat of precursor reaction) at least one blowing agent in the presenceof a nucleating agent as described above, at least one organicpolyisocyanate and at least one compound containing at least tworeactive hydrogen atoms. In making a polyisocyanate-based foam, thepolyisocyanate, reactive hydrogen-containing compound, and blowing agentcomposition can generally be combined, thoroughly mixed (using, e.g.,any of the various known types of mixing head and spray apparatus), andpermitted to expand and cure into a cellular polymer. It is oftenconvenient, but not necessary, to preblend certain of the components ofthe foamable composition prior to reaction of the polyisocyanate and thereactive hydrogen-containing compound. For example, it is often usefulto first blend the reactive hydrogen-containing compound, blowing agentcomposition, and any other components (e.g., surfactant) except thepolyisocyanate, and to then combine the resulting mixture with thepolyisocyanate. Alternatively, all components of the foamablecomposition can be introduced separately. It is also possible topre-react all or a portion of the reactive hydrogen-containing compoundwith the polyisocyanate to form a prepolymer.

In some embodiments, the present disclosure is directed to dielectricfluids that include one or more hydrofluoroether compounds of thepresent disclosure, as well as to electrical devices (e.g., capacitors,switchgear, transformers, or electric cables or buses) that include suchdielectric fluids. For purposes of the present application, the term“dielectric fluid” is inclusive of both liquid dielectrics and gaseousdielectrics. The physical state of the fluid, gaseous or liquid, isdetermined at the operating conditions of temperature and pressure ofthe electrical device in which it is used.

In some embodiments, the dielectric fluids include one or morehydrofluoroether compounds of the present disclosure and, optionally,one or more second dielectric fluids. Suitable second dielectric fluidsinclude, for example, air, nitrogen, helium, argon, and carbon dioxide,or combinations thereof. The second dielectric fluid may be anon-condensable gas or an inert gas. Generally, the second dielectricfluid may be used in amounts such that vapor pressure is at least 70 kPaat 25° C., or at the operating temperature of the electrical device.

The dielectric fluids of the present application are useful forelectrical insulation and for arc quenching and current interruptionequipment used in the transmission and distribution of electricalenergy. Generally, there are three major types of electrical devices inwhich the fluids of the present disclosure can be used: (1)gas-insulated circuit breakers and current-interruption equipment, (2)gas-insulated transmission lines, and (3) gas-insulated transformers.Such gas-insulated equipment is a major component of power transmissionand distribution systems.

In some embodiments, the present disclosure provides electrical devices,such as capacitors, comprising metal electrodes spaced from each othersuch that the gaseous dielectric fills the space between the electrodes.The interior space of the electrical device may also comprise areservoir of the liquid dielectric fluid which is in equilibrium withthe gaseous dielectric fluid. Thus, the reservoir may replenish anylosses of the dielectric fluid.

In some embodiments, the present disclosure relates to coatingcompositions that include a solvent composition that one or morehydrofluoroether compounds of the present disclosure, and one or morecoating materials which are soluble or dispersible in the solventcomposition.

In various embodiments, the coating materials of the coatingcompositions may include pigments, lubricants, stabilizers, adhesives,anti-oxidants, dyes, polymers, pharmaceuticals, release agents,inorganic oxides, and the like, and combinations thereof. For example,coating materials may include perfluoropolyether, hydrocarbon, andsilicone lubricants; amorphous copolymers of tetrafluoroethylene;polytetrafluoroethylene; or combinations thereof. Further examples ofsuitable coating materials include titanium dioxide, iron oxides,magnesium oxide, perfluoropolyethers, polysiloxanes, stearic acid,acrylic adhesives, polytetrafluoroethylene, amorphous copolymers oftetrafluoroethylene, or combinations thereof.

In some embodiments, the above-described coating compositions can beuseful in coating deposition, where the hydrofluoroether compoundfunction as a carrier for a coating material to enable deposition of thematerial on the surface of a substrate. In this regard, the presentdisclosure further relates to a process for depositing a coating on asubstrate surface using the coating composition. The process comprisesthe step of applying to at least a portion of at least one surface of asubstrate a coating of a liquid coating composition comprising (a) asolvent composition containing one or more hydrofluoroether compounds ofthe present disclosure; and (b) one or more coating materials which aresoluble or dispersible in the solvent composition. The solventcomposition can further comprise one or more co-dispersants orco-solvents and/or one or more additives (e.g., surfactants, coloringagents, stabilizers, anti-oxidants, flame retardants, and the like).Preferably, the process further comprises the step of removing thesolvent composition from the coating by, e.g., allowing evaporation(which can be aided by the application of, e.g., heat or vacuum).

In various embodiments, to form a coating composition, the components ofthe coating composition (i.e., the hydrofluoroether compound(s), thecoating material(s), and any co-dispersant(s) or co-solvent(s) utilized)can be combined by any conventional mixing technique used fordissolving, dispersing, or emulsifying coating materials, e.g., bymechanical agitation, ultrasonic agitation, manual agitation, and thelike. The solvent composition and the coating material(s) can becombined in any ratio depending upon the desired thickness of thecoating. For example, the coating material(s) may constitute from about0.1 to about 10 weight percent of the coating composition.

In illustrative embodiments, the deposition process of the disclosurecan be carried out by applying the coating composition to a substrate byany conventional technique. For example, the composition can be brushedor sprayed (e.g., as an aerosol) onto the substrate, or the substratecan be spin-coated. In some embodiments, the substrate may be coated byimmersion in the composition. Immersion can be carried out at anysuitable temperature and can be maintained for any convenient length oftime. If the substrate is a tubing, such as a catheter, and it isdesired to ensure that the composition coats the lumen wall, thecomposition may be drawn into the lumen by the application of reducedpressure.

In various embodiments, after a coating is applied to a substrate, thesolvent composition can be removed from the coating (e.g., byevaporation). If desired, the rate of evaporation can be accelerated byapplication of reduced pressure or mild heat. The coating can be of anyconvenient thickness, and, in practice, the thickness will be determinedby such factors as the viscosity of the coating material, thetemperature at which the coating is applied, and the rate of withdrawal(if immersion is utilized).

Both organic and inorganic substrates can be coated by the processes ofthe present disclosure. Representative examples of the substratesinclude metals, ceramics, glass, polycarbonate, polystyrene,acrylonitrile-butadiene-styrene copolymer, natural fibers (and fabricsderived therefrom) such as cotton, silk, fur, suede, leather, linen, andwool, synthetic fibers (and fabrics) such as polyester, rayon, acrylics,nylon, or blends thereof, fabrics including a blend of natural andsynthetic fibers, and composites of the foregoing materials. In someembodiments, substrates that may be coated include, for example,magnetic hard disks or electrical connectors with perfluoropolyetherlubricants or medical devices with silicone lubricants.

In some embodiments, the present disclosure relates to cleaningcompositions that include one or more hydrofluoroether compounds of thepresent disclosure, and one or more co-solvents.

In some embodiments, the hydrofluoroether compounds may be present in anamount greater than 50 weight percent, greater than 60 weight percent,greater than 70 weight percent, or greater than 80 weight percent basedupon the total weight of the hydrofluoroether compounds and theco-solvent(s).

In various embodiments, the cleaning composition may further comprise asurfactant. Suitable surfactants include those surfactants that aresufficiently soluble in the fluorinated olefin, and which promote soilremoval by dissolving, dispersing or displacing the soil. One usefulclass of surfactants are those nonionic surfactants that have ahydrophilic-lipophilic balance (HLB) value of less than about 14.Examples include ethoxylated alcohols, ethoxylatedalkyl phenols,ethoxylated fatty acids, alkylarysulfonates, glycerol esters,ethoxylated fluoroalcohols, and fluorinated sulfonamides. Mixtures ofsurfactants having complementary properties may be used in which onesurfactant is added to the cleaning composition to promote oily soilremoval and another added to promote water-soluble oil removal. Thesurfactant, if used, can be added in an amount sufficient to promotesoil removal. Typically, surfactant is added in amounts from about 0.1to 5.0 wt. %, preferably in amounts from about 0.2 to 2.0 wt. % of thecleaning composition.

In illustrative embodiments, the co-solvent may include alcohols,ethers, alkanes, alkenes, haloalkenes, perfluorocarbons, perfluorinatedtertiary amines, perfluoroethers, cycloalkanes, esters, ketones,aromatics, haloaromatics, siloxanes, hydrochlorocarbons,hydrochlorofluorocarbons, hydrochlorofluoroolefins, hydrofluorocarbons,or mixtures thereof. Representative examples of co-solvents which can beused in the cleaning composition include methanol, ethanol, isopropanol,t-butyl alcohol, methyl t-butyl ether, methyl t-amyl ether,1,2-dimethoxyethane, cyclohexane, 2,2,4-trimethylpentane, n-decane,terpenes (e.g., a-pinene, camphene, and limonene),trans-1,2-dichloroethylene, cis-1,2-dichloroethylene,methylcyclopentane, decalin, methyl decanoate, t-butyl acetate, ethylacetate, diethyl phthalate, 2-butanone, methyl isobutyl ketone,naphthalene, toluene, p-chlorobenzotrifluoride, trifluorotoluene,bis(trifluoromethyl)benzenes, hexamethyl disiloxane, octamethyltrisiloxane, perfluorohexane, perfluoroheptane, perfluorooctane,perfluorotributylamine, perfluoro-N-methyl morpholine, perfluoro-2-butyloxacyclopentane, methylene chloride, chlorocyclohexane, 1-chlorobutane,1,1-dichloro-1-fluoroethane, 1,1,1-trifluoro-2,2-dichloroethane,1,1,1,2,2-pentafluoro-3,3-dichloropropane,1,1,2,2,3-pentafluoro-1,3-dichloropropane, 2,3-dihydroperfluoropentane,1,1,1,2,2,4-hexafluorobutane,1-trifluoromethyl-1,2,2-trifluorocyclobutane,3-methyl-1,1,2,2-tetrafluorocyclobutane, 1-hydropentadecafluoroheptane,or mixtures thereof.

In some embodiments, the present disclosure relates to a process forcleaning a substrate. The cleaning process can be carried out bycontacting a contaminated substrate with a cleaning composition asdiscussed above. The hydrofluoroether compounds can be utilized alone orin admixture with each other or with other commonly-used cleaningsolvents, e.g., alcohols, ethers, alkanes, alkenes, perfluorocarbons,perfluorinated tertiary amines, perfluoroethers, cycloalkanes, esters,ketones, aromatics, siloxanes, hydrochlorocarbons,hydrochlorofluorocarbons, hydrochlorofluoroolefins, hydrofluoroolefins,hydrofluorocarbons, or mixtures thereof. Such co-solvents can be chosento modify or enhance the solvency properties of a cleaning compositionfor a particular use and can be utilized in ratios (of co-solvent tohydrofluoroether compounds) such that the resulting composition has noflash point. If desirable for a particular application, the cleaningcomposition can further contain one or more dissolved or dispersedgaseous, liquid, or solid additives (for example, carbon dioxide gas,surfactants, stabilizers, antioxidants, or activated carbon).

In some embodiments, the present disclosure relates to cleaningcompositions that include one or more hydrofluoroether compounds of thepresent disclosure and optionally one or more surfactants. Suitablesurfactants include those surfactants that are sufficiently soluble inthe hydrofluoroether compounds, and which promote soil removal bydissolving, dispersing or displacing the soil. One useful class ofsurfactants are those nonionic surfactants that have ahydrophilic-lipophilic balance (HLB) value of less than about 14.Examples include ethoxylated alcohols, ethoxylated alkylphenols,ethoxylated fatty acids, alkylaryl sulfonates, glycerol esters,ethoxylated fluoroalcohols, and fluorinated sulfonamides. Mixtures ofsurfactants having complementary properties may be used in which onesurfactant is added to the cleaning composition to promote oily soilremoval and another added to promote water-soluble soil removal. Thesurfactant, if used, can be added in an amount sufficient to promotesoil removal. Typically, surfactant may be added in amounts from 0.1 to5.0 wt. % or from 0.2 to 2.0 wt. % of the cleaning composition.

The cleaning processes of the disclosure can also be used to dissolve orremove most contaminants from the surface of a substrate. For example,materials such as light hydrocarbon contaminants; higher molecularweight hydrocarbon contaminants such as mineral oils and greases;fluorocarbon contaminants such as perfluoropolyethers,bromotrifluoroethylene oligomers (gyroscope fluids), andchlorotrifluoroethylene oligomers (hydraulic fluids, lubricants);silicone oils and greases; solder fluxes; particulates; water; and othercontaminants encountered in precision, electronic, metal, and medicaldevice cleaning can be removed.

The cleaning compositions can be used in either the gaseous or theliquid state (or both), and any of known or future techniques for“contacting” a substrate can be utilized. For example, a liquid cleaningcomposition can be sprayed or brushed onto the substrate, a gaseouscleaning composition can be blown across the substrate, or the substratecan be immersed in either a gaseous or a liquid composition. Elevatedtemperatures, ultrasonic energy, and/or agitation can be used tofacilitate the cleaning. Various different solvent cleaning techniquesare described by B. N. Ellis in Cleaning and Contamination ofElectronics Components and Assemblies, Electrochemical PublicationsLimited, Ayr, Scotland, pages 182-94 (1986).

Both organic and inorganic substrates can be cleaned by the processes ofthe present disclosure. Representative examples of the substratesinclude metals; ceramics; glass; polycarbonate; polystyrene;acrylonitrile-butadiene-styrene copolymer; natural fibers (and fabricsderived therefrom) such as cotton, silk, fur, suede, leather, linen, andwool; synthetic fibers (and fabrics) such as polyester, rayon, acrylics,nylon, or blends thereof; fabrics comprising a blend of natural andsynthetic fibers; and composites of the foregoing materials. In someembodiments, the process may be used in the precision cleaning ofelectronic components (e.g., circuit boards), optical or magnetic media,or medical devices.

In some embodiments, the present disclosure further relates toelectrolyte compositions that include one or more hydrofluoroethercompounds of the present disclosure. The electrolyte compositions maycomprise (a) a solvent composition including one or more of thehydrofluoroether compounds; and (b) at least one electrolyte salt. Theelectrolyte compositions of the present disclosure exhibit excellentoxidative stability, and when used in high voltage electrochemical cells(such as rechargeable lithium ion batteries) provide outstanding cyclelife and calendar life. For example, when such electrolyte compositionsare used in an electrochemical cell with a graphitized carbon electrode,the electrolytes provide stable cycling to a maximum charge voltage ofat least 4.5V and up to 6.0V vs. Li/Li⁺.

Electrolyte salts that are suitable for use in preparing the electrolytecompositions of the present disclosure include those salts that compriseat least one cation and at least one weakly coordinating anion (theconjugate acid of the anion having an acidity greater than or equal tothat of a hydrocarbon sulfonic acid (for example, abis(perfluoroalkanesulfonyl)imide anion); that are at least partiallysoluble in a selected hydrofluoroether compound (or in a blend thereofwith one or more other hydrofluoroether compounds or one or moreconventional electrolyte solvents); and that at least partiallydissociate to form a conductive electrolyte composition. The salts maybe stable over a range of operating voltages, are non-corrosive, and arethermally and hydrolytically stable. Suitable cations include alkalimetal, alkaline earth metal, Group JIB metal, Group IIIB metal,transition metal, rare earth metal, and ammonium (for example,tetraalkylammonium

or trialkylammonium) cations, as well as a proton. In some embodiments,cations for battery use include alkali metal and alkaline earth metalcations. Suitable anions include fluorine-containing inorganic anionssuch as (FSO₂)₂N⁻, BF₄ ⁻, PF₆ ⁻, AsF₆ ⁻, and SbF₆ ⁻; CIO₄ ⁻; HSO₄ ⁻;H₂PO₄ ⁻; organic anions such as alkane, aryl, and alkaryl sulfonates;fluorine-containing and nonfluorinated tetraarylborates; carboranes andhalogen-, alkyl-, or haloalkylsubstituted carborane anions includingmetallocarborane anions; and fluorine-containing organic anions such asperfluoroalkanesulfonates, cyanoperfluoroalkanesulfonylamides,bis(cyano)perfluoroalkanesulfonylmethides,bis(perfluoroalkanesulfonyl)imides,bis(perfluoroalkanesulfonyl)methides, andtris(perfluoroalkanesulfonyl)methides; and the like. Preferred anionsfor battery use include fluorine-containing inorganic anions (forexample, (FSO₂)₂N⁻, BF₄ ⁻, PF₆ ⁻, and AsF₆ ⁻) and fluorine-containingorganic anions (for example, perfluoroalkanesulfonates,bis(perfluoroalkanesulfonyl)imides, andtris(perfluoroalkanesulfonyl)methides). The fluorine-containing organicanions can be either fully fluorinated, that is perfluorinated, orpartially fluorinated (within the organic portion thereof). In someembodiments, the fluorine-containing organic anion is at least about 80percent fluorinated (that is, at least about 80 percent of thecarbon-bonded substituents of the anion are fluorine atoms). In someembodiments, the anion is perfluorinated (that is, fully fluorinated,where all of the carbon-bonded substituents are fluorine atoms). Theanions, including the perfluorinated anions, can contain one or morecatenary heteroatoms such as, for example, nitrogen, oxygen, or sulfur.In some embodiments, fluorine-containing organic anions includeperfluoroalkanesulfonates, bis(perfluoroalkanesulfonyl)imides, andtris(perfluoroalkanesulfonyl)methides.

In some embodiments, the electrolyte salts may include lithium salts.Suitable lithium salts include, for example, lithiumhexafluorophosphate, lithium bis(trifluoromethanesulfonyl)imide, lithiumbis(perfluoroethanesulfonyl)imide, lithium tetrafluoroborate, lithiumperchlorate, lithium hexafluoroarsenate, lithiumtrifluoromethanesulfonate, lithiumtris(trifluoromethanesulfonyl)methide, lithium bis(fluorosulfonyl)imide(Li—FSI), and mixtures of two or more thereof.

The electrolyte compositions of the present disclosure can be preparedby combining at least one electrolyte salt and a solvent compositionincluding at least one hydrofluoroether compound of the presentdisclosure, such that the salt is at least partially dissolved in thesolvent composition at the desired operating temperature. Thehydrofluoroether compounds (or a normally liquid composition including,consisting, or consisting essentially thereof) can be used in suchpreparation.

In some embodiments, the electrolyte salt is employed in the electrolytecomposition at a concentration such that the conductivity of theelectrolyte composition is at or near its maximum value (typically, forexample, at a Li molar concentration of around 0.1-4.0 M, or 1.0-2.0 M,for electrolytes for lithium batteries), although a wide range of otherconcentrations may also be employed.

In some embodiments, one or more conventional electrolyte solvents aremixed with the hydrofluoroether compound(s) (for example, such that thehydrofluoroether(s) constitute

from about 1 to about 80 or 90 percent of the resulting solventcomposition). Useful conventional electrolyte solvents include, forexample, organic and fluorine-containing electrolyte solvents (forexample, propylene carbonate, ethylene carbonate, dimethyl carbonate,diethyl carbonate, ethyl methyl carbonate, dimethoxyethane,7-butyrolactone, diglyme (that is, diethylene glycol dimethyl ether),tetraglyme (that is, tetraethylene glycol dimethyl ether),monofluoroethylene carbonate, vinylene carbonate, ethyl acetate, methylbutyrate, tetrahydrofuran, alkyl-substituted tetrahydrofuran, 1,3-dioxolane, alkyl-substituted 1, 3-dioxolane, tetrahydropyran,alkyl-substituted tetrahydropyran, and the like, and mixtures thereof).Other conventional electrolyte additives (for example, a surfactant) canalso be present, if desired.

The present disclosure further relates to electrochemical cells (e.g.,fuel cells, batteries, capacitors, electrochromic windows) that includethe above-described electrolyte compositions. Such an electrochemicalcell may include a positive electrode, a negative electrode, aseparator, and the above-described electrolyte composition.

An electrochemical device using the electrolyte compositions describedherein may, in some embodiments, have a discharge capacity of greaterthan 50%, preferably greater than 80% of theoretical, at a dischargecurrent of up to 12 C. An electrochemical cell including the electrolytecomposition described in this disclosure may, in some embodiments, havea charge capacity of greater than about 40%, preferably greater thanabout 60% of theoretical, at a charge current of up to 6 C. Anelectrochemical cell including the electrolyte compositions describedherein may, in some embodiments, have excellent low temperatureperformance, and may retain over 90% of its discharge capacity at 25° C.when exposed to ambient temperatures from 0° C. to −20° C. Theelectrochemical cell including the presently described electrolytecompositions may, in some embodiments, retain a discharge capacity ofgreater than 150 mAh per gram of cathode over up to 30 charging cyclesat up to 4.5V.

A variety of negative and positive electrodes may be employed in theelectrochemical cells. Representative negative electrodes includegraphitic carbons e. g., those having a spacing between (002)crystallographic planes, d₀₀₂, of 3.45 A>d₀₀₂>3.354 A and existing informs such as powders, flakes, fibers or spheres (e. g., mesocarbonmicrobeads); Li_(4/3)Ti_(5/3)O₄ the lithium alloy compositions describedin U.S. Pat. No. 6,203,944 (Turner '944) entitled “ELECTRODE FOR ALITHIUM BATTERY” and PCT Published Patent Application No. WO 00103444(Turner PCT) entitled “ELECTRODE MATERIAL AND COMPOSITIONS”; andcombinations thereof. Representative positive electrodes includeLiFePO₄, LiMnPO₄, LiCoPO₄, LiMn₂O₄, LiCoO₂ and combinations thereof. Thenegative or positive electrode may contain additives such as will befamiliar to those skilled in the art, e. g., carbon black for negativeelectrodes and carbon black, flake graphite and the like for positiveelectrodes.

The electrochemical devices of the invention can be used in variouselectronic articles such as computers, power tools, automobiles,telecommunication devices, and the like.

Embodiments

1. A hydrofluoroether compound represented by the following generalformula (1):

wherein n is 1-2, and each occurrence of Rf₁ and Rf₂ is:

-   -   (i) independently a linear or branched perfluoroalkyl group        having 1-8 carbon and optionally comprises one or more catenated        heteroatoms; or    -   (ii) bonded together to form a ring structure having 4-8 carbon        atoms and optionally comprises one or more catenated        heteroatoms; and

Rfh is, when n=1, a substituted or unsubstituted, monovalent,hydrocarbon group having 1-12 carbon atoms optionally comprising one ormore catenary heteroatoms and, when n=2, a substituted or unsubstituted,divalent, hydrocarbon group having 1-12 carbon atoms optionallycomprising one or more catenary heteroatoms.

2. The hydrofluoroether compound according to embodiment 1, wherein eachoccurrence of Rf₁ and Rf₂ is:(i) independently a linear or branched perfluoralkyl group having 1-4carbons and optionally comprises one or more catenated heteroatoms; or(ii) bonded together to form a ring structure having 4-6 or carbon atomsand optionally comprises one or more catenated heteroatoms.3. The hydrofluoroether compound according to any one of the previousembodiments, wherein Rfh is substituted with halogen atoms.4. The hydrofluoroether compound according to any one of the previousembodiments, wherein Rfh is substituted with fluorine atoms.5. The hydrofluoroether compound according to any one of the previousembodiments, wherein the hydrofluoroether compound has a degree offluorination that is at least 60%.7. A fire extinguishing composition comprising:

(a) a hydrofluoroether compound according to any one of embodiments 1-5;

(b) at least one co-extinguishing agent comprising one or morehydrofluorocarbons, hydrochlorofluorocarbons, perfluorocarbons,perfluoropolyethers, hydrofluoroethers, hydrofluoropolyethers,chlorofluorocarbons, bromofluorocarbons, bromochlorofluorocarbons,iodofluorocarbons, hydrobromofluorocarbons, fluorinated ketones,hydrobromocarbons, fluorinated olefins, hydrofluoroolefins, fluorinatedsulfones, fluorinated vinylethers, and mixtures thereof,

wherein (a) and (b) are present in an amount sufficient to suppress orextinguish a fire.

8. A fire extinguishing composition according to embodiment 7, wherein(a) and (b) are in a weight ratio of from about 9:1 to about 1:9.9. A method of extinguishing a fire comprising:

applying to the fire a fire extinguishing composition comprising ahydrofluoroether compound according to any one of embodiments 1-5; and

suppressing the fire.

10. A method of extinguishing a fire according to embodiment 9, whereinthe fire extinguishing composition further comprises at least oneco-extinguishing agent comprising one or more hydrofluorocarbons,hydrochlorofluorocarbons, perfluorocarbons, perfluoropolyethers,hydrofluoroethers, hydrofluoropolyethers, chlorofluorocarbons,bromofluorocarbons, bromochlorofluorocarbons, iodofluorocarbons,hydrobromofluorocarbons, fluorinated ketones, hydrobromocarbons,fluorinated olefins, hydrofluoroolefins, fluorinated sulfones,fluorinated vinylethers, and mixtures thereof.11. An apparatus for converting thermal energy into mechanical energy ina Rankine cycle comprising:

a working fluid;

a heat source to vaporize the working fluid and form a vaporized workingfluid;

a turbine through which the vaporized working fluid is passed therebyconverting thermal energy into mechanical energy;

a condenser to cool the vaporized working fluid after it is passedthrough the turbine; and

a pump to recirculate the working fluid,

wherein the working fluid comprises a hydrofluoroether compoundaccording to any one of embodiments 1-5.

12. A process for converting thermal energy into mechanical energy in aRankine cycle comprising:

vaporizing a working fluid with a heat source to form a vaporizedworking fluid;

expanding the vaporized working fluid through a turbine;

cooling the vaporized working fluid using a cooling source to form acondensed working fluid; and

pumping the condensed working fluid;

wherein the working fluid comprises a hydrofluoroether compoundaccording to any one of embodiments 1-5.

13. A process for recovering waste heat comprising:

passing a liquid working fluid through a heat exchanger in communicationwith a process that produces waste heat to produce a vaporized workingfluid;

removing the vaporized working fluid from the heat exchanger;

passing the vaporized working fluid through an expander, wherein thewaste heat is converted into mechanical energy; and

cooling the vaporized working fluid after it has been passed through theexpander;

wherein the working fluid comprises a hydrofluoroether compoundaccording to any one of embodiments 1-5.

14. A foamable composition comprising:

a blowing agent;

a foamable polymer or a precursor composition thereof; and

a nucleating agent, wherein said nucleating agent comprises ahydrofluoroether compound according to any one of embodiments 1-5.

15. A foamable composition according to embodiment 14, wherein thenucleating agent and the blowing agent are in a molar ratio of less than1:2.16. A foamable composition according to any one of embodiments 14-15,wherein the blowing agent comprises an aliphatic hydrocarbon having fromabout 5 to about 7 carbon atoms, a cycloaliphatic hydrocarbon havingfrom about 5 to about 7 carbon atoms, a hydrocarbon ester, water, orcombinations thereof.17. A process for preparing polymeric foam comprising:

vaporizing at least one liquid or gaseous blowing agent or generating atleast one gaseous blowing agent in the presence of at least one foamablepolymer or a precursor composition thereof and a nucleating agent,wherein said nucleating agent comprises a hydrofluoroether compoundingaccording to any one of embodiments 1-5.

18. A foam made with the foamable composition according to any one ofembodiments 14-16.19. A device comprising:

a dielectric fluid comprising a hydrofluoroether compound according toany one of embodiments 1-5;

wherein the device is an electrical device.

20. The device of embodiment 15, wherein said electrical devicecomprises a gas-insulated circuit breakers, current-interruptionequipment, a gas-insulated transmission line, a gas-insulatedtransformers, or a gas-insulated substation.21. The device according to any one of embodiments 19-20, wherein thedielectric fluid further comprises a second dielectric gas.22. The device of embodiment 21, wherein the second dielectric gascomprises an inert gas.23. The device of embodiment 22, wherein the second dielectric gascomprises nitrogen, helium, argon, or carbon dioxide.24. A coating composition comprising:

a solvent composition comprising a hydrofluoroether compound accordingto any one of embodiments 1-5; and

a coating material that is soluble or dispersible in said solventcomposition.

25. The coating composition according to embodiment 24, wherein saidcoating material comprises a pigment, lubricant, stabilizer, adhesive,anti-oxidant, dye, polymer, pharmaceutical, release agent, inorganicoxide.26. The composition according to embodiment 24, wherein said coatingmaterial comprises a perfluoropolyether, a hydrocarbon, a siliconelubricant, a copolymer of tetrafluoroethylene, or apolytetrafluoroethylene.27. A cleaning composition comprising:

a hydrofluoroether compound according to any one of embodiments 1-5; and

a co-solvent.

28. The composition of embodiment 27, wherein said hydrofluoroethercompound is greater than 50 percent by weight of said composition basedon the total weights of the fluorinated compound and the co-solvent.29. The composition according to any one of embodiments 27-28, whereinsaid co-solvent comprises alcohols, ethers, alkanes, alkenes,haloalkenes, perfluorocarbons, perfluorinated tertiary amines,perfluoroethers, cycloalkanes, esters, ketones, aromatics,haloaromatics, siloxanes, hydrochlorocarbons, hydrochlorofluorocarbons,hydrochlorofluorolefins, hydrofluoroolefins, hydrofluorocarbons, ormixtures thereof.30. A cleaning composition comprising:

a hydrofluoroether compound according to any one of embodiments 1-5; and

a surfactant.

31. The cleaning composition of embodiment 30, wherein the cleaningcomposition comprises from 0.1 to 5 percent by weight surfactant.32. The composition according to any one of embodiments 30-31, whereinthe surfactant comprises a nonionic surfactant comprising an ethoxylatedalcohol, an ethoxylated alkylphenol, an ethoxylated fatty acid, analkylaryl sulfonate, a glycerolester, an ethoxylated fluoroalcohol, afluorinated sulfonamide, or mixtures thereof.33. A process for removing contaminants from a substrate, the processcomprising the steps of:

contacting a substrate with a composition comprising:

-   -   a hydrofluoroether compound according to any one of embodiments        1-5; and    -   a co-solvent.        34. An electrolyte composition comprising:

a solvent composition comprising at least one hydrofluoroether compoundaccording to any one of embodiments 1-5; and

an electrolyte salt.

The operation of the present disclosure will be further described withregard to the following detailed examples. These examples are offered tofurther illustrate various embodiments and techniques. It should beunderstood, however, that many variations and modifications may be madewhile remaining within the scope of the present disclosure.

EXAMPLES Example 1: Synthesis of O(CF₂CF₂)₂NCFHCF₂OCH₃,2,2,3,3,5,5,6,6-octafluoro-4-(1,2,2-trifluoro-2-methoxy-ethyl)morpholine

Perfluoro-vinylmorpholine (200.00 g, 0.6430 mol) and anhydrous methanol(200.00 g, 6.242 mol) were charged to a 1.0 L 3-necked round bottomedflask equipped with a magnetic stir bar, water cooled condenser,nitrogen inlet line, and a 60 mL addition funnel. A 5.0 Molar solutionof sodium methoxide in methanol (40.0 g, 0.2147 mol) was charged to theaddition funnel and added dropwise over a one hour period with stirringto the reaction mixture starting at 21° C. A slightly exothermicreaction ensued, causing the reaction mixture to reach a maximumtemperature of 52° C. with no external cooling. After a reaction time of3 hours at 21-52° C., the reaction appeared to be complete judging fromthe disappearance of the lower perfluoro-vinylmorpholine liquid phase,but the reaction was allowed to continue with stirring at roomtemperature for another three days. Analysis of the reaction mixture byGC-FID and GC-MS revealed 100% conversion of theperfluoro-vinylmorpholine to 87% desired HFE-Hydride,O(CF₂CF₂)₂NCFHCF₂OCH₃, and 9% of the corresponding HFE-Olefin,O(CF₂CF₂)₂NCF═CFOCH₃ (cis and trans mixture). This reaction mixture wasquenched with 500 mL of water at room temperature with stirringproducing two non-miscible liquid phases. The pH of the reaction mixturewas adjusted to approximately neutral (pH 5) by addition of 2.3 grams of34.4% H₃PO_(4(aq)) and the reaction mixture was transferred to a 1.0 Lseparatory funnel. The lower fluorochemical phase was isolated and thenwashed with three 400 mL portions of deionized water. After the finalwater wash the isolated lower fluorochemical phase (193.8 g) wastransferred to a dry Erlenmeyer flask and dried over 3 A molecularsieves. The dried fluorochemical phase was then transferred to 250 mL,3-necked round bottomed flask equipped with a 40-plate concentric tubedistillation column and distillation head and purified by fractionaldistillation under a nitrogen atmosphere at atmospheric pressure. Themain product cuts (158.5 g) were collected at 125.7-127.7° C. (headtemperature) and consisted of about 96% desired HFE-Hydride,O(CF₂CF₂)₂NCFHCF₂OCH₃, the remainder comprising mainly the HFE-Olefinbyproduct, O(CF₂CF₂)₂NCF═CFOCH₃ (cis and trans mixture) by GC.

An approximately 95:5 mixture of O(CF₂CF₂)₂NCFHCF₂OCH₃ andO(CF₂CF₂)₂NCF═CFOCH₃ prepared as described above (213.5 g, 0.622 mol)was transferred to a 250 mL HDPE polybottle equipped with magneticstirring bar and treated neat (no solvent) with anhydrous hydrogenfluoride (13.0 g, 0.65 mol) with stirring at room temperature. Thismixture was allowed to stir for 3 days at room temperature in theloosely capped polybottle followed by quenching (dropwise initially tocontrol exotherm) with deionized water (88.0 g). The resulting two-phasemixture was transferred to a Teflon separatory funnel and the lowerfluorochemical phase was isolated and then washed with three 128 mLportions of deionized water to remove residual HF. After the final waterwash, the lower fluorochemical product phase (209.1 g) was drained to adry Erlenmeyer flask and dried over 3 A molecular sieves. After dryingovernight, the fluorochemical product was analyzed by GC-FID, revealingthat HF addition to the HFE-Olefin byproduct, O(CF₂CF₂)₂NCF═CFOCH₃, wascomplete and the product was 98.7% pure HFE-Hydride,O(CF₂CF₂)₂NCFHCF₂OCH₃. No residual HFE-Olefin byproduct was detected.This material was then fractionally distilled as before to remove otherimpurities. The main product distillation cuts (Fractions 3, 4 and 5,190.10 g total) distilled at 127.0-127.3° C. and had a GC purityof >99%. GC peak assignments were confirmed by GC-MS and the purity ofcombined cuts 4 and 5 (120.6 g) determined by quantitative ¹H and ¹⁹FNMR spectroscopy was 99.3% by wt overall (sum of three desired productisomers, absolute wt %), including 99.1 wt % O(CF₂CF₂)₂NCFHCF₂OCH₃ plustwo minor isomers. The purified O(CF₂CF₂)₂NCFHCF₂OCH₃ product was anon-viscous liquid at room temperature and was determined to benon-flammable (no closed cup flash point up to 200° F.). It had ameasured density of 1.64 g/mL, a specific heat capacity (measured by DSCat room temperature) of 0.25 calories/gram° C. and an estimated Log KOW(oil/water partition coefficient measured by HPLC) of 4.46. The 4 hourLC-50 and the NOAEL (No Observable Adverse Effect Level) in maleSprague-Dawley rats were both determined to be >5000 ppm (v/v), based onacute inhalation toxicity testing in animals dosed at 5000 ppm for 4hours. All animals survived and appeared normal during 14 day post doserecovery period. Aside from slightly increased respiration rates during4 hour dosing, no significant clinical observations or body or organweight effects were noted.

Example 2: Synthesis of O(CF₂CF₂)₂NCFHCF₂OCH₂CF₂CF₂H,2,2,3,3,5,5,6,6-octafluoro-4-[1,2,2-trifluoro-2-(2,2,3,3-tetrafluoropropoxy)ethyl]morpholine

The reagents2,2,3,3,5,5,6,6-octafluoro-4-(1,2,2-trifluorovinyl)morpholine (179.11 g,98.9% pure by GC), 2,2,3,3-tetrafluoropropanol (80.687 g, TCI America,98.0%), and 543 mL of acetonitrile (Aldrich, Anyhydrous) were combinedin a 3-necked, 1000 mL round bottom flask equipped with magneticstirring, a Teflon coated thermocouple probe, and a water-cooledcondenser with N₂ inlet. The reaction mixture was initially biphasic.Then potassium carbonate (8.445 g, 325 mesh, Armand Product Co) wasadded batch-wise to the reaction mixture at room temperature withstirring. A wet ice bath was placed around reaction vessel to controlthe reaction exotherm and keep the reaction temperature near 25° C.After stirring for 2 hours the reaction mixture was analyzed by GC-FIDand the reaction was found to be 95.3% complete. After 4 hours anadditional 0.075 g of powdered potassium carbonate was charged to thereaction mixture and stirred for an additional 30 minutes prior toGC-FID analysis, which indicated that the reaction was greater than99.5% complete. Once the reaction was essentially complete, the reactionmixture was filtered through a sintered glass fritted funnel by suctionto remove insoluble solids. The filtered reaction mix was transferred toa 1000 mL round bottomed flask and acetonitrile solvent was removed byfractional distillation. After nearly all the acetonitrile (and residualHCF₂CF₂CH₂OH) was removed, the yield of crude product remaining in thepot was 197.01 g. GC-FID analysis of the pot retains indicates that thecrude product comprises 80.98% desired HFE-Hydride,O(CF₂CF₂)₂NCFHCF₂OCH₂CF₂CF₂H, and 17.0% HFE-Olefin byproduct,O(CF₂CF₂)₂NCF═CFOCH₂CF₂CF₂H (cis and trans isomers). The crudefluorochemical product mixture was transferred to a 250 mL HDPEpolybottle equipped with a magnetic stir bar and treated with excessanhydrous HF (˜90 grams). The polybottle was loosely capped and themixture stirred magnetically at room temperature for 72 hours. Theremaining anhydrous HF was then quenched and diluted with 90 mL water(added dropwise initially, to control exotherm). The resulting two-phaseliquid mixture was transferred to a Teflon reparatory funnel and thelower fluorochemical product phase (196.9 g) was separated from theupper aqueous HF phase. The fluorochemical phase was then washed withthree 100 mL portions of water to remove residual HF from the productphase. The pH of the final water wash was 7.0 and the yield of crudefluorochemical product after washing was 191.5 g. GC-FID analysis ofthis material indicates that the HF treatment has reduced the level ofHFE-Olefin byproducts (cis and trans isomers) to only 0.76%, the balancebeing mostly (97.89%) desired HFE-Hydride. This material was transferredto an HDPE poly bottle and stored over 3 A molecular sieves to dry.After storing over molecular sieves for a minimum of 48 hours the crudefluorochemical product was purified by fractional distillation undernitrogen at atmospheric pressure using a 40-plate concentric tubedistillation column and a distillation head equipped with a water-cooledcondenser and liquid splitter. The main product distillation cuts(Fractions 8-12) were collected at 164.2-164.9° C. (head temperature)and consisted of >98% pure HFE-Hydride, O(CF₂CF₂)₂NCFHCF₂OCH₂CF₂CF₂H.The highest purity distillation cut (Fraction 10) was analyzed by GC-MS,which confirmed that the desired HFE-Hydride product was present in ˜99%purity. Quantitative analysis of this material by ¹H and ¹⁹F NMRspectroscopy showed that the final product contained 99.17% (absolute wt%) of the desired HFE-Hydride, O(CF₂CF₂)₂NCFHCF₂OCH₂CF₂CF₂H.

The acute single dose oral toxicity of O(CF₂CF₂)₂NCFHCF₂OCH₂CF₂CF₂H wasexamined in rats dosed at 300 mg/kg body weight. No adverse clinicalobservations were noted during the post dose recovery period andnecropsy results were normal for all animals. Based on this study, theLD₅₀ of2,2,3,3,5,5,6,6-octafluoro-4-[1,2,2-trifluoro-2-(2,2,3,3-tetrafluoropropoxy)ethyl]morpholineis estimated to be >300 mg/kg body weight.

Example 3: Synthesis of O(CF₂CF₂)₂NCFHCF₂OCH₂CH₂OCH₃,2,2,3,3,5,5,6,6-octafluoro-4-[1,2,2-trifluoro-2-(2-methoxy)ethyl]morpholine

The reagents2,2,3,3,5,5,6,6-octafluoro-4-(1,2,2-trifluorovinyl)morpholine (200.00g, >98.9%), acetonitrile (236 g, Aldrich Anhydrous, 99.8%), potassiumhydroxide (3.608 g, powdered, Fluka, >85%) and sodium bromide (6.616 g,granular, EMD, 99%) were combined in a 3-neck 1000 mL round bottom flaskequipped with overhead stirring, a water cooled condenser with N₂ inlet,a Claisen adapter with Teflon coated thermocouple probe and an additionfunnel. While the reaction mixture was stirring, 2-methoxy-ethanol(76.09 g, TCI America, 98%) was charged to the reaction mixture over 3hours. A slightly exothermic reaction was observed causing the reactiontemperature to rise to 26° C. The reaction was stirred for 2 hoursfollowing addition of all the alcohol before a sample was removed bypipette, filtered through a PVDF filter disc and analyzed by GC-FID. GCanalysis indicated that the desired reaction had proceeded to 93%conversion. The reaction mixture was stirred for an additional 4 hoursand then quenched with 400 mL deionized water and 100 g of concentratedsodium chloride brine solution. The fluorochemical product separatedfrom aqueous solution forming a lower liquid phase. The fluorochemicalphase was isolated and washed with three additional 200 mL portions ofwater to remove residual acetonitrile and then dried over molecularsieves for a minimum of three days. After drying, the crudefluorochemical product was treated with 30 g anhydrous hydrofluoric acidto remove the minor olefinic byproducts,4-[(E&Z)-1,2-difluoro-2-(2-methoxyethoxy)vinyl]-2,2,3,3,5,5,6,6-octafluoro-morpholine,and convert them to the desired HF addition product. The HF treatmentwas allowed to proceed overnight at room temperature with magneticstirring in a well ventilated and scrubbed fume hood. The followingmorning, residual HF was removed by quenching with 125 mL of water(adding the water dropwise initially to control exotherm), isolating thelower fluorochemical product phase and then washing with three 125 mLportions of water to remove residual HF (pH of final aqueous wash was6.5). Once isolated, the crude fluorochemical product was dried againover molecular sieves for a minimum of three days and then purified byfractional distillation through a concentric tube distillation columngiving 76.46 g of product distillate (B.P.=177-178° C.) as a clearcolorless liquid with an average purity of 99.41% by GC-FID. Theidentity of the product was confirmed by GC/MS and the chemicalstructure and purity was verified by quantitative ¹⁹F and ¹H NMRspectroscopy showing that the distillate consisted of 99 wt %2,2,3,3,5,5,6,6-octafluoro-4-[1,2,2-trifluoro-2-(2-methoxy)ethyl]morpholine.

Examples 4-30: Vial Reactions of Perfluorinated Vinyl Amines withVarious Alcohols

The following examples were prepared by the following general method:K₂CO₃ powder, anhydrous CH₃CN, perfluoro-vinylamine and the alcoholreagent were charged to a 7 mL glass vial in the order indicated (inair). A mini stir bar was added and the vial was then tightly capped andrapid stirring initiated at the temperature indicated in the Table. Thereaction was allowed to proceed with stirring for a minimum 4 hours,while monitoring the progress of the reaction periodically by GC-FID byremoving small aliquots of the reaction mixture and injecting neat. Oncethe reaction was judged to be nearly complete, the reaction solution wasfiltered by syringe to remove suspended solids and the filtrate wassubmitted for GC-MS analysis to confirm tentative GC-FID peakassignments and identify the major products formed. This information wasthen used to calculate the GC yield of the desired alcohol additionproducts (sum of the HFE-Hydride+HFE-Olefin) and the Hydride/Olefinratio. The results are summarized in the Table below and demonstratethat perfluorinated vinyl amines react with various alcohols generallyin high yield to produce mainly the desired HFE-Hydrides, with the majorbyproduct being the corresponding HFE-Olefins. The HFE-Olefin byproductsare readily converted to the desired HFE-Hydride by treatment withanhydrous hydrogen fluoride as shown in the Examples above. Thus thesereactions provide a high yield and selective route to HFE-Hydrides.

TABLE Reactions of Perfluorinated Vinyl Amines with Various AlcoholsCH3CN Rxn Reaction GC Area % Hydride/ K2CO3 Solvent Time Temp Yield ofOlefin Ex PF-Vinylamine mMoles Alcohol mMoles (mMoles) (mLs) (Hrs) ° C.Desired * Ratio **  4

3.22 CF3CH2OH 3.38 0.34 3 67 21 89 4.9  5

3.22 HCF2CF2CH2OH 3.38 0.34 3 36 22 90 4.7  6

3.22 CF3CFHCF2CH2OH 3.38 0.34 3 4 22 90 5.9  7

3.22 C2F5CH2OH 3.38 0.34 3 4 22 94 4.8  8

3.22 (CF3)2CHOH 3.38 0.34 3 4 22 90 3.7  9

3.22 CF3CFHCF2CH(CH3)OH 3.38 0.34 3 4 22 96 1.4 10

8.00 HOCH2CF2CF2CH2OH 4.00 0.60 3 18 40 74 1.1 11

5.14 CH2═CHCH2OH 6.17 0.51 1 48 21 60 No Olefin detected 12

5.14 HC≡CCH2OH 6.17 0.51 1 48 21 63 No Olefin detected 13

5.14 (CH3)2NCH2CH2OH 6.17 0.51 1 24 21 57 15.9  14

5.14 HOCH2CH(CH2)2 6.17 0.51 1 24 21 85 7.6 15

5.14 HOCH2CH2OCH3 6.17 0.51 1 24 21 71 3.0 16

5.14 HO(CH2)2OH 6.17 0.51 1 24 21 63 4.3 17

6.43 HOC2H4OC2H4OH 3.06 0.60 5 18 21 40 3.3 18

6.43 HOCH2CH═CHCH2OH 3.06 0.60 5 24 21 9 No Olefin detected 19

3.22 CH3OH 6.50 0.34 3 92 21 76 NA 20

3.22 CH3CH2OH 6.50 0.34 3 92 21 63 0.9 21

3.22 (CH3)2CHOH 6.50 0.34 3 92 21 2 NA 22

3.00 HCF2CF2CH2OH 3.30 0.30 3 18 21 84 1.4 23

3.00 CF3CH2OH 3.30 0.30 3 19 21 85 1.6 24

3.00 (CF3)2CHOH 3.30 0.30 3 21 21 79 0.9 25

6.01 HOC2H4OC2H4OH 2.86 0.30 5 22 21 31 0.8 26

6.01 HOCH2CH═CHCH2OH 2.86 0.30 5 40 21 11 0.9 27

6.01 HOC4H8OH 2.86 0.30 5 22 21 21 0.6 28

3.20 CH3OH 4.70 0.40 4 24 21 73 5.6 29

4.00 CH3CH2OH 4.00 0.41 4 24 21 87 2.9 30

5.14 HO(CH2)4OH 6.17 0.51 1 24 21 29 1.9 * Based on conversion ofPF-Vinylamine to desired HFE-Hydride (major) and HFE-Olefin (minor)addition products by GC-FID. ** HFE-Hydride to HFE-Olefin ratiodetermined from relative GC-FID peak areas. NA means unable to quantifyHydride/Olefin ratio due to overlapping GC peaks. Yields areunoptimized. Yields reported for the difunctional alcohols,HOCH₂CF₂CF₂CH₂OH, HOCH₂CH₂OH, HOCH₂CH₂OCH₂CH₂OH, HOCH₂CH═CHCH₂OH, andHO(CH₂)₄OH are for the bis-addition products only.

Using the procedure and reagents described in Examples 4-30, thefollowing hydrofluoroether (or HFE-Hydride) compounds were successfullyprepared and characterized by GC-MS:

Ex Product  4

 5

 6

 7

 8

 9

10

11

12

13

14

15

16

17

18

19

20

21

22

23

24

25

26

27

28

29

30

Example 31: Solubility of Various Solutes in2,2,3,3,5,5,6,6-octafluoro-4-(1,2,2-trifluoro-2-methoxy-ethyl)morpholineVs. Other Commercial HFE Solvents

The maximum solubility of various solutes, including common lubricantsand additives, was measured in2,2,3,3,5,5,6,6-octafluoro-4-(1,2,2-trifluoro-2-methoxy-ethyl)morpholinesolvent and compared with the solubility of the same solutes in twocommercially available, non-flammable, HFE solvents, including asegregated HFE (Novec 7100) and a non-segregated HFE (PF-7600), bothavailable from 3M Company, St. Paul Minn. The data was collected at roomtemperature and is summarized in the Table below. This data demonstratesthat2,2,3,3,5,5,6,6-octafluoro-4-(1,2,2-trifluoro-2-methoxy-ethyl)morpholine,a nitrogen-containing HFE-Hydride of the present invention, providesequivalent or superior solubility characteristics for many of thesolutes tested and is an especially good solvent for relatively polarsolutes.

TABLE Solubility of Solutes in Fluorinated Solvents (Maximum Wt % Solutein Fluorinated Solvent) Fluorinated Solvent           Solutes          Solute Type

        PF-7600 (Comp)         Novec-7100 (Comp) Fomblin Z-DolPerfluoropolyether lube >10% >10%  >10% Fomblin Z-TetraolPerfluoropolyether lube   1.8%   1.0%   0.3% Moresco D40HPerfluoropolyether lube   1.5% —   0.5% Dow Corning 556Methylphenylpolysiloxane 8-11% * 3-6% Miscible Dow Corning 200Polydimethylsiloxane <0.8% <0.2% <0.3% (350cSt) Mineral Oil WhiteNonpolar Hydrocarbon <0.5% <0.2% <0.2% (Light) Dioctyl Phthalate PolarHydrocarbon >30% >30% 5.4-5.8% * Soluble at 50:50 wt ratio (50% by Wt)as well

Example 32: Solubility of2,2,3,3,5,5,6,6-octafluoro-4-(1,2,2-trifluoro-2-methoxy-ethyl)morpholineand2,2,3,3,5,5,6,6-octafluoro-4-[1,2,2-trifluoro-2-(2,2,3,3-tetrafluoropropoxy)ethyl]morpholinein Common Li Ion Battery Electrolyte Formulations Vs. Novec-7300

The maximum solubility of two nitrogen-containing HFE-Hydrides of thepresent invention was determined in a commonly employed carbonate-basedsolvent formulation (EC:EMC 3:7 by wt) used in lithium ion batteryelectrolytes and a similar electrolyte formulation containing 1.0M LiPF₆(a commonly employed electrolyte salt). The solubility of thesenitrogen-containing HFE-Hydrides in the two battery electrolyteformulations was compared to the solubility of Novec-7300, acommercially available segregated HFE that has been previously studiedas a battery electrolyte cosolvent. The relative solubility data wascollected at room temperature and is summarized in the Table below. Thisdata demonstrates that the nitrogen containing HFE-Hydrides of thepresent invention have significantly better solubility in theserelatively polar battery electrolyte formulations compared toNovec-7300. Thus, the nitrogen-containing HFE-Hydrides of the presentinvention represent promising battery electrolyte cosolvents that canprovide improved formulation flexibility due to their enhancedsolubility in commonly used electrolyte formulations.

TABLE Solubility of HFE Cosolvents in LIB Electrolyte Formulations (MaxWt % HFE in electrolyte) 1.0M LiPF₆ in EC:EMC EC:EMC HFE Cosolvent 3:7by Wt 3:7 by Wt

>40% 22%

>40% 55% Novec-7300 (Comp) <20%  6%

Example 33: Comparative Toxicity of2,2,3,3,5,5,6,6-octafluoro-4-(1,2,2-trifluoro-2-methoxy-ethyl)morpholineVs. Other Non-segregated HFEs

The acute inhalation toxicity of2,2,3,3,5,5,6,6-octafluoro-4-(1,2,2-trifluoro-2-methoxy-ethyl)morpholinein rats was determined by dosing animals at 5000 ppm for 4 hoursfollowed by 14 day post-dose monitoring. Based on the animal testresults and the vapor pressure (VP) of the test compound, the LC-50, NoObservable Effect Level (NOEL), and the Acute Vapor Hazard Ratio wereestimated. These values are summarized in the Table below and comparedto other common non-segregated HFEs for which similar toxicity and vaporpressure (VP) data is available. In terms of these standard measures oftoxicity,2,2,3,3,5,5,6,6-octafluoro-4-(1,2,2-trifluoro-2-methoxy-ethyl)morpholinecompares quite favorably to the other non-segregated HFEs and is amongthe least toxic materials tested.

TABLE Comparative Toxicity of2,2,3,3,5,5,6,6-octafluoro-4-(1,2,2-trifluoro-2-methoxy-ethyl)morpholine Vs. Other Non-segregated HFEs Acute VP VP Vapor LC50(LD50) data - LC50 (mmHg) (atm) Hazard Compound Structure inhalationNOAEL/NOEL data Value at 25 C. at 25 C. Ratio* Ex #1O(CF₂CF₂)NCFHCF₂OCH₃ LC50 >5000 ppm NOEL >5000 ppm 5000 15.8 0.0208 4(rat, inhalation) - 3M (rat, inhalation) - 3M OIME (CF₃)₂CHCF₂OCH₃ LC50660 ppm [NOAEL must be 660 127.9 0.1683 255 (mouse, inhalation) - <660ppm (mouse, Daikin SDS inhalation) by inference] AE-3000 CF₃CH₂OCF₂CF₂HLC50 3010 ppm NOEL 1000 ppm 3010 233 0.3066 102 (acute rat, inhal) -(90d inhalation) - AGC SDS AGC SDS NOEL <1500 ppm (rat inhalation, 1h) -3M 301-monohydride CF₃CFHCF₂OCH₃ LC50 >10,000 ppm [NOAEL must be 10000174 0.2289 23 (rat, inhal, 5d) - 3M <10,000 ppm (rat inhal, 5d) byinference] Novec 7600 CF₃CFHCF₂CH(CH₃)OCF₂CFHCF₃ LC50 (rat, inhalation,NOEL (rat, inhalation, 2000 7 0.0092 5 4h), >2000 ppm - 3M 29d) <500 ppm*Vapor Hazard Ratio Reference:Popendorf, W., Am. Ind. Hyg. Assoc. J, 45(10), 719-726, (1984)

Other embodiments of the invention are within the scope of the appendedclaims.

1. A hydrofluoroether compound represented by the following generalformula (1):

wherein n is 1-2, and each occurrence of Rf₁ and Rf₂ is: (i)independently a linear or branched perfluoroalkyl group having 1-8carbon and optionally comprises one or more catenated heteroatoms; or(ii) bonded together to form a ring structure having 4-8 carbon atomsand optionally comprises one or more catenated heteroatoms; and Rfh is,when n=1, a substituted or unsubstituted, monovalent, hydrocarbon grouphaving 1-12 carbon atoms optionally comprising one or more catenaryheteroatoms and, when n=2, a substituted or unsubstituted, divalent,hydrocarbon group having 1-12 carbon atoms optionally comprising one ormore catenary heteroatoms.
 2. The hydrofluoroether compound according toclaim 1, wherein each occurrence of Rf₁ and Rf₂ is: (i) independently alinear or branched perfluoralkyl group having 1-4 carbons and optionallycomprises one or more catenated heteroatoms; or (ii) bonded together toform a ring structure having 4-6 or carbon atoms and optionallycomprises one or more catenated heteroatoms.
 3. The hydrofluoroethercompound according to claim 1, wherein Rfh is substituted with halogenatoms.
 4. The hydrofluoroether compound according to claim 1, whereinRfh is substituted with fluorine atoms.
 5. The hydrofluoroether compoundaccording to claim 1, wherein the hydrofluoroether compound has a degreeof fluorination that is at least 60%.
 6. The hydrofluoroether compoundaccording to claim 1, wherein the hydrofluoroether compound isrepresented by one or more of the following formulas:


7. A working fluid comprising a hydrofluoroether compound according toclaim 1, wherein the hydrofluoroether compound is present in the workingfluid at an amount of at least 50% by weight based on the total weightof the working fluid.
 8. An apparatus for heat transfer comprising: adevice; and a mechanism for transferring heat to or from the device, themechanism comprising a heat transfer fluid that comprises ahydrofluoroether compound according to claim
 1. 9. An apparatus for heattransfer according to claim 8, wherein the device is selected from amicroprocessor, a semiconductor wafer used to manufacture asemiconductor device, a power control semiconductor, an electrochemicalcell, an electrical distribution switch gear, a power transformer, acircuit board, a multi-chip module, a packaged or unpackagedsemiconductor device, a fuel cell, and a laser.
 10. An apparatus forheat transfer according to claim 8, wherein the mechanism fortransferring heat is a component in a system for maintaining atemperature or temperature range of an electronic device.
 11. A methodof transferring heat comprising: providing a device; and transferringheat to or from the device using a heat transfer fluid that comprises ahydrofluoroether compound according to claim 1.